Dynamic micro-interface polymerization method of two-dimensional polymer material and application of dynamic micro-interface polymerization method in preparation of quasi-solid electrolyte

Abstract

The invention provides a dynamic micro-interface polymerization method of a two-dimensional polymer material and application of the dynamic micro-interface polymerization method in preparation of a quasi-solid electrolyte, and the dynamic micro-interface polymerization method comprises the following steps: adding a first reaction monomer into a solvent, and stirring to obtain a first monomer solution; adding a second reaction monomer into the solvent, and stirring to obtain a second monomer solution; adding the second monomer solution into the reaction container, injecting the first monomer solution into the second monomer solution under a stirring condition, and reacting to obtain a mixed system; and carrying out suction filtration, purification and drying on the mixed system to obtain the two-dimensional polymer material. According to the dynamic micro-interface polymerization method disclosed by the invention, a dynamic micro-interface reaction system with a huge specific surface area is constructed through external mechanical stirring, and a reaction place is expanded from a limited two-dimensional plane to a massive micron-scale interface in a three-dimensional space, so that the core defect of insufficient interface area in static interface polymerization is fundamentally overcome.

Description

Technical Field

[0001] This invention belongs to the field of chemical engineering, and in particular relates to a dynamic micro-interface polymerization method for two-dimensional polymer materials and its application in the preparation of quasi-solid electrolytes. Background Technology

[0002] Organic two-dimensional materials are a class of layered materials with thicknesses ranging from molecules to nanometers and macroscopic lateral dimensions. Their two-dimensional frameworks are typically composed of organic molecular building blocks linked by strong covalent or coordination bonds, mainly including two-dimensional polymers, covalent organic frameworks, and metal-organic frameworks. Currently, the preparation of these materials mainly follows two basic strategies: top-down and bottom-up approaches. The top-down strategy involves the physical dissociation of layered bulk precursors through mechanical exfoliation or solvent intercalation to obtain two-dimensional materials. Conversely, the bottom-up strategy relies on the self-assembly and polymerization of molecular building blocks driven by topological symmetry, or polymerization within a two-dimensional confined space, to directly synthesize two-dimensional structures. Among these, interfacial polymerization technology provides an effective route for the preparation of two-dimensional materials by guiding monomer reactions at phase interfaces.

[0003] Interfacial polymerization is an important thin film preparation strategy in the synthesis of two-dimensional organic materials. Among them, traditional static interfacial polymerization is a relatively mature method. This method is based on an oil-water two-phase system, utilizing the stable liquid-liquid interface formed therein as the reaction site. Different monomers contact and polymerize at the interface to form two-dimensional thin film materials.

[0004] However, this process is limited by the small contact area between the two phases and low mass transfer efficiency, resulting in insufficient contact and conversion of monomers. This not only leads to low product yield but also increases raw material costs due to the large amount of unreacted monomers remaining, severely limiting its potential for large-scale industrial applications.

[0005] To improve the yield and monomer conversion rate of two-dimensional material synthesis, recent research has focused on optimizing interfacial polymerization processes, mainly including the following methods: (1) Use of phase transfer catalyst (PTC): promotes the diffusion of aqueous reactants into the organic phase and improves reaction efficiency; (2) Surface synthesis method: Solvent-free polymerization is carried out on a solid surface (such as Ag(111)) to achieve precise editing of polymer chain sequence by utilizing the two-dimensional confinement effect; (3) Application of interfacial photothermal catalysis: By using local photothermal effect and in-situ separation of products, the reaction equilibrium limitation is broken, thereby improving the conversion rate and reducing the excess demand for reactants; Although the above strategies have improved the interface aggregation process to varying degrees, they generally face common problems such as high control difficulty, high equipment requirements, difficulty in scaling up, and high costs, resulting in significant bottlenecks in industrialization and cost control. Summary of the Invention

[0006] In view of this, the present invention aims to overcome the defects in the prior art and proposes a dynamic micro-interface polymerization method for two-dimensional polymer materials and its application in the preparation of quasi-solid electrolytes.

[0007] To achieve the above objectives, the technical solution of the present invention is implemented as follows: A dynamic micro-interface polymerization method for two-dimensional polymer materials includes the following steps: (1) Add the first reactant monomer to the solvent and stir until the first reactant monomer is completely dissolved to obtain the first monomer solution; (2) Add the second reactant to the solvent and stir until the second reactant is completely dissolved to obtain a solution of the second reactant; (3) The second monomer solution is added to the reaction vessel, and the first monomer solution is injected into the second monomer solution under stirring. After the reaction is completed, a reaction mixture system is obtained. (4) After filtering, purifying and drying the reaction mixture, the two-dimensional polymer material is obtained.

[0008] Further, in step (1), the first reactant monomer is at least one of acyl chloride monomers, sulfonyl chloride monomers, isocyanate monomers, epoxy resin monomers, aldehyde monomers, vinyl aromatic monomers, or imidazole monomers; the acyl chloride monomer is trimesoyl chloride or cyclohexane-1,3,5-tricarboxyl chloride; the sulfonyl chloride monomer is 1,3,6-naphthalenetrisulfonyl chloride or 1,3,5-benzenetrisulfonyl chloride; the isocyanate monomer is triphenylmethane triisocyanate or toluene-2,6-diisocyanate; the epoxy resin monomer is epoxy silicone resin or glycerol epoxy resin; the aldehyde monomer is terephthalaldehyde or trimesoyl chloride; the vinyl aromatic monomer is 1,4-divinylbenzene or 1,3,5-trivinylbenzene; and the imidazole monomer is 2-methylimidazolium or benzimidazole. The solvent in step (1) is at least one of n-hexane, cyclohexane, n-heptane, isooctane, dichloromethane, chloroform, toluene, o-xylene, chlorobenzene or anisole; the concentration of the first monomer solution in step (1) is 0.10-3.00 mol / L.

[0009] Furthermore, the stirring step in step (1) has a rotation speed of 100-900 rpm, a time of 10-90 minutes, and a temperature of 20-60℃.

[0010] Further, the second reaction monomer in step (2) is at least one of an amine monomer, an alcohol monomer, a thiol monomer, a carboxylic acid monomer, or a metal salt monomer; the amine monomer is at least one of polyetheramine, 1,4-butanediamine, 1,2,3-propanetriamine, or ethylene glycol bis(3-aminopropyl) ether; the alcohol monomer is 1,3,5-pentanetriol or ethylene glycol; the thiol monomer is 1,3-propanedithiol or triazine trithiol; the carboxylic acid monomer is 1,3,5-pentanetricarboxylic acid or succinic acid; and the metal salt monomer is zinc nitrate or copper acetate. The solvent in step (2) is at least one of water, methanol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide or ionic liquid; the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-benzyl-3-methylimidazolium dicyandiamide; the concentration of the second monomer solution in step (2) is 0.10-5.00 mol / L.

[0011] Furthermore, the stirring step in step (2) has a rotation speed of 100-900 rpm, a time of 10-90 minutes, and a temperature of 20-60℃.

[0012] Furthermore, the stirring step in step (3) has a rotation speed of 100-400 rpm, a time of 20-80 minutes, and a temperature of 23-27℃.

[0013] During the stirring process, the stirring generates shear force on the two-phase fluid, dispersing the two immiscible phases into a large number of droplets. At this time, the surface of each droplet is the reaction interface between the two phases, i.e., a dynamic micro-interface. Continuous stirring ensures that the droplets do not agglomerate and the interface is dynamically updated.

[0014] As the amidation reaction proceeds (as shown in Formula I), amide bonds gradually connect to form polymer chains. Due to the large micro-interface area, a large number of acyl chloride monomers and amine monomers can react simultaneously at the interface, and the polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0015] Formula I As the Hinsburg reaction proceeds (as shown in Formula II), a large number of sulfonyl chloride monomers and amine monomers can react simultaneously at the interface, and the polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0016]

[0017] Formula II As the nucleophilic addition reaction proceeds, a large number of isocyanate monomers and compounds containing active hydrogen (such as amines, alcohols, and carboxylic acid monomers) can react simultaneously at the interface. The polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0018] As the curing reaction proceeds, a large number of epoxy resin monomers and compounds containing active hydrogen (such as amines and alcohols) can react simultaneously at the interface. The polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0019] As the Schiff base reaction proceeds, a large number of aldehyde monomers and amine monomers can react simultaneously at the interface, and the polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0020] As the click chemoaddition reaction proceeds, a large number of vinyl aromatic monomers and thiol monomers can react simultaneously at the interface, and the polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0021] As the coordination reaction proceeds, a large number of metal salt monomers and imidazole monomers can react simultaneously at the interface, and the polymer chains grow rapidly and aggregate to form a two-dimensional sheet-like structure, which is eventually suspended in the dispersed phase.

[0022] Furthermore, in step (3), the volume ratio of the first monomer solution to the second monomer solution is 1:5-5:1.

[0023] Furthermore, the filter membrane used in step (4) of the filtration step has a pore size of 0.1-0.45 mm. The polytetrafluoroethylene filter membrane is m; the drying step in step (4) is performed at a temperature of 40-70°C for 6-12 hours.

[0024] Furthermore, the purification step in step (4) is as follows: anhydrous ethanol is added to the crude product after filtration, and after magnetic stirring, vacuum filtration is performed. The solid is collected and washed with ethanol.

[0025] A two-dimensional polymer material prepared using the preparation method described above.

[0026] An application of a two-dimensional polymer material, specifically its application in the preparation of quasi-solid-state electrolytes.

[0027] In this invention, the probability of monomer contact and reaction is greatly increased, the huge interface area provides a large number of reactive sites, and the monomer diffusion distance is shortened from the centimeter level of the traditional static method to the micrometer level, enabling monomers to quickly reach the interface to participate in the reaction.

[0028] Meanwhile, the reactants are in more complete contact, and the reaction rate is changed from "diffusion control" in the traditional method to "reaction kinetic control", which significantly improves the conversion rate of monomers and the yield of the final product, and reduces raw material waste from the source.

[0029] Furthermore, the method is simple to operate, the reaction process is easy to control and scale up, and continuous stirring ensures that the reaction conditions (temperature and concentration) on the surface of each droplet are basically the same, resulting in a consistent polymerization rate. The resulting two-dimensional material has excellent and stable properties, providing a feasible technical path for large-scale production.

[0030] To address the common technical bottlenecks in existing quasi-solid-state electrolytes, such as low ionic conductivity, poor compatibility with electrode interfaces, and difficulty in large-scale preparation, this invention provides a systematic solution using two-dimensional polymer nanosheets prepared through dynamic micro-interface polymerization technology as a substrate. Firstly, the well-organized two-dimensional sheet structure of the nanosheets allows for orderly stacking, forming efficient ion transport channels and laying the structural foundation for high ionic conductivity. Secondly, the excellent film-forming properties of the nanosheets enable the formation of smooth films, effectively reducing interfacial impedance and improving compatibility with electrode materials. Thirdly, the assembly of the nanosheets supports various processes such as vacuum filtration, blade coating, roller coating, and spray coating, and can be directly formed into large-area self-supporting films, seamlessly connecting to existing roll-to-roll production lines to achieve large-scale preparation of quasi-solid-state electrolytes.

[0031] Compared with the prior art, the present invention has the following advantages: The dynamic micro-interface polymerization method for two-dimensional polymer materials described in this invention constructs a dynamic micro-interface reaction system with a huge specific surface area through external mechanical stirring, expanding the reaction site from a limited two-dimensional plane to a massive number of micron-scale interfaces in three-dimensional space, fundamentally overcoming the core defect of insufficient interface area in static interface polymerization.

[0032] The dynamic micro-interface polymerization method for two-dimensional polymer materials described in this invention aims to significantly improve the monomer conversion rate and reaction efficiency in the synthesis process of two-dimensional materials. It is a feasible path to achieve high-yield, controllable, and large-scale preparation of organic two-dimensional materials, so as to meet the urgent needs of their industrial application in fields such as high-performance devices.

[0033] The dynamic micro-interface polymerization method for two-dimensional polymer materials described in this invention is designed for specific combinations of process parameters for the preparation of two-dimensional thin films, including the concentration of the first monomer solution, the concentration of the second monomer solution, the reaction speed, the reaction temperature, and the reaction time. The above parameter combination can achieve a monomer conversion rate of over 90% and stable product performance.

[0034] The dynamic micro-interface polymerization method for two-dimensional polymer materials described in this invention can be applied to the preparation of various organic two-dimensional materials (such as two-dimensional polyamides, two-dimensional polyurethanes, two-dimensional metal-organic frameworks, etc.). By replacing monomers with different reaction types (such as acyl chlorides, amines, isocyanates, metal ions, etc.), high conversion rates and high yields can be achieved. Attached Figure Description

[0035] Figure 1 Morphological characterization of the PEO-BTA nanosheets described in Example 1 of the present invention: Figure a is a scanning electron microscope (SEM) image, Figure b is the lateral size distribution data obtained from the SEM images, Figure c is an atomic force microscope (AFM) image, and Figure d is the height profile curve corresponding to the line segment shown in Figure c. Figure 2 The following are SEM images of PEO-BTA nanosheets without mechanical stirring as described in Example 1 of the present invention: Figure a is a surface morphology image, and Figure b is a cross-sectional morphology image. Figure 3 The transverse dimensions and thickness of the PEO-BTA nanosheets described in this embodiment of the invention vary with ( Figure 3 a) Stirring speed and ( Figure 3 b) Relationship between the concentrations of 1,3,5-benzenetricarbonyl trichloride (TMC) and poly(propylene glycol)bis(2-aminopropyl ether) monomers (PEA); Figure 4 The TMC monomer conversion rate determination based on the standard calibration curve method described in this embodiment of the invention is shown in Figure a, which is a TMC-n-hexane solution with known concentrations (0.01-0.05 mmol / L) and a solution obtained by diluting the residual unreacted TMC solution after polymerization by 800 times (marked as "unknown sample"). Figure b shows the linear relationship between absorbance at 226 nm wavelength and TMC concentration. Figure 5 The following are morphological images of two-dimensional sheet products prepared by dynamic micro-interface polymerization of monomers with different reaction types according to embodiments of the present invention: Figure a is a TEM image of the polymerization product obtained by the Hinsburg reaction of sulfonyl chloride monomers and amine monomers; Figure b is a TEM image of the polymerization product obtained by the nucleophilic addition reaction of isocyanate monomers and alcohol monomers; Figure c is a TEM image of the polymerization product obtained by the curing reaction of epoxy resin monomers and amine monomers; Figure d is a TEM image of the polymerization product obtained by the Schiff base reaction of aldehyde monomers and amine monomers; Figure e is a TEM image of the polymerization product obtained by the click chemistry reaction of vinyl aromatic monomers and thiol monomers; Figure f is a TEM image of the polymerization product obtained by the coordination reaction of imidazole monomers and metal salt monomers. Figure 6 The following is a schematic diagram illustrating the application of the two-dimensional polymer described in this invention in the preparation of quasi-solid electrolytes: Figure a is a photograph of a large-area PEO-BTA dry film prepared by a blade coating process, Figure b is a photograph of a 16 mm diameter circular PEO-BTA sample, and Figure c is an electrochemical impedance spectroscopy of the PEO-BTA quasi-solid electrolyte. Detailed Implementation

[0036] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0037] The present invention will be described in detail below with reference to the embodiments.

[0038] Example 1 A dynamic micro-interface polymerization method for two-dimensional polymer materials includes the following steps: (1) Analytical grade TMC was added to n-hexane and stirred at room temperature (200 rpm) for 10 minutes until TMC was completely dissolved, resulting in a TMC-n-hexane solution with a concentration of 0.3 mol / L and a total volume of 6.0 mL; (2) Add industrial grade PEA to 1-butyl-3-methylimidazolium tetrafluoroborate and stir at room temperature (300 rpm) for 15 minutes until PEA is completely dissolved to obtain a PEA-ionic liquid solution with a concentration of 1.0 mol / L and a total volume of 3.0 mL; (3) Add the PEA-ionic liquid solution to a 50 mL reaction vessel, and inject the TMC-n-hexane solution into the PEA-ionic liquid solution under stirring at room temperature (300 rpm). The reaction time is 30 minutes. After the polymerization reaction is completed, a reaction mixture is obtained. (4) Select a pore size of 0.22 for the reaction mixture system. The polytetrafluoroethylene (PTFE) filter membrane was used for vacuum filtration, and the solid product (coarse PEO-BTA sheets) on the filter membrane was collected. 100 mL of anhydrous ethanol was added and magnetically stirred to dissolve the remaining unreacted TMC (soluble in ethanol), n-hexane (soluble in ethanol), and ionic liquid (partially soluble in ethanol) in the ethanol. Vacuum filtration was then performed again, and the solid was collected. The ethanol washing-filtration operation was repeated 3 times to ensure that the impurities were completely removed. The purified solid was dried at 60°C for 12 hours to obtain a uniform two-dimensional PEO-BTA sheet product.

[0039] Figure 1SEM images of a show that PEO-BTA exhibits a typical two-dimensional sheet-like morphology. Statistical data on the lateral size distribution of a large number of PEO-BTA sheets are also presented. Figure 1 b) indicates that the average lateral dimension of the lamellae is approximately 75. m. AFM image ( Figure 1 c) further confirmed the two-dimensional morphology of PEO-BTA, and the corresponding height profile curve ( Figure 1 d) indicates that the thickness of the two-dimensional PEO-BTA sheet is approximately 20 nm.

[0040] Figure 2 SEM images of PEO-BTA products without mechanical stirring are shown. The images reveal that the thickness of this type of product reaches 5 mm. The membrane surface exhibits highly uneven morphology and roughness, displaying obvious agglomeration and uneven stacking. This further demonstrates that, in the absence of dynamic micro-interface construction, polymerization reactions can only occur within a limited interface, easily leading to local monomer enrichment and polymerization, resulting in thick and structurally inhomogeneous products. This also indirectly confirms that the dynamic micro-interface introduced by mechanical stirring is key to achieving uniform, ultrathin two-dimensional nanosheet structures, highlighting the significant advantages of this patented technology in controlling material morphology and size.

[0041] Experimental Example 1 The transverse dimensions and thickness of the product were measured at stirring speeds of 100 rpm, 300 rpm, 500 rpm, and 700 rpm in step (3), respectively. The results are as follows: Figure 3 As shown in figure a, in the low rotational speed ranges of 100 rpm and 300 rpm, the lateral dimensions and thickness of the two-dimensional PEO-BTA nanosheets are almost unaffected by the rotational speed, with average values ​​remaining at 75 rpm. m and 20 nm. When the rotation speed was increased to 500 rpm and then further increased to 700 rpm, the lateral dimension of the two-dimensional PEO-BTA nanosheets decreased to 33 nm. m and 23 The nanosheets have a diameter of 10 nm, while the thickness increases significantly to 44 nm and 88 nm. The decrease in the lateral size of the nanosheets is due to the accelerated dynamic renewal rate of the micro-interface at higher rotation speeds, while the increase in thickness is due to the increased diffusion rate of monomers to the micro-interface at higher rotation speeds, which in turn accelerates the reaction process.

[0042] The transverse dimensions and thickness of the product were measured when the concentration of the TMC-n-hexane solution in step (1) was 0.06 mol / L, the concentration of the PEA-ionic liquid solution in step (2) was 0.2 mol / L, the concentration of the TMC-n-hexane solution in step (2) was 0.3 mol / L, the concentration of the PEA-ionic liquid solution in step (2) was 1.0 mol / L, the concentration of the TMC-n-hexane solution in step (2) was 1.5 mol / L, and the concentration of the PEA-ionic liquid solution in step (2) was 5.0 mol / L. The results are as follows. Figure 3 As shown in b, despite the initial monomer concentrations spanning two orders of magnitude, the average lateral size and thickness of the two-dimensional PEO-BTA nanosheets remained consistently at 75. The nanometers are around 20 nm. However, their structural uniformity varies significantly with concentration: in low-concentration systems (0.06 mol / L TMC-n-hexane solution, 0.20 mol / L PEA-ionic liquid solution), the standard deviation of the lateral dimensions of the two-dimensional PEO-BTA nanosheets is 2.38 nm. The standard deviation of the thickness was 0.34 nm; in high-concentration systems (1.50 mol / L TMC-n-hexane solution, 5.0 mol / L PEA-ionic liquid solution), the standard deviation of the lateral dimensions of the nanosheets was 0.39 nm. The standard deviation of the thickness was 0.45 nm; in medium concentration systems (0.30 mol / L TMC-n-hexane solution, 1.0 mol / L PEA-ionic liquid solution), the standard deviations of both the lateral dimension and thickness of the nanosheets were the lowest, decreasing to 0.27 nm. The values ​​of m and 0.29 nm indicate that the two-dimensional PEO-BTA nanosheets prepared at moderate concentrations have the most uniform structure. This is because the monomer diffusion and polymerization reactions at the micro-interface reach a dynamic equilibrium. At low concentrations, the reactive sites are sparsely and unevenly distributed, which easily leads to large fluctuations in product size; while at high concentrations, random aggregation of monomers is triggered, ultimately resulting in a rough morphology of the nanosheets.

[0043] Experimental Example 2 The UV absorption spectra of the TMC solutions were measured when the concentrations of the TMC-n-hexane solution in step (1) were 0.01 mmol / L, 0.02 mmol / L, 0.03 mmol / L, 0.04 mmol / L, 0.05 mmol / L, and the solution obtained after diluting the residual unreacted TMC solution 800 times (labeled as "unknown sample"). The results are as follows: Figure 4 As shown in Figure a, the maximum absorbance monotonically increases with increasing TMC solution concentration, and the peak value of the unknown sample is closest to that of the 0.03 mmol / L TMC solution. For accurate quantification, a standard calibration curve was further plotted using absorbance at 226 nm versus TMC concentration, as shown in Figure a. Figure 4 As shown in b, the absorbance and concentration at this wavelength exhibit a good linear relationship. Substituting the absorbance of the unknown sample into the fitting equation yields the concentration of the unknown sample. Multiplying this by the dilution factor (800 times) gives the concentration of the unreacted TMC solution remaining after polymerization. The conversion rate of TMC is calculated to be 93% based on the difference in TMC concentration before and after polymerization.

[0044] Experiment Example 3 Two-dimensional sheet-like products were prepared by dynamic micro-interface polymerization using monomers with different reaction types, as detailed below: 1. Polymerization of sulfonyl chloride monomers and amine monomers - Hinesburg reaction The first reactant in step (1) is 1,3,5-benzenetrisulfonyl chloride; the solvent is cyclohexane.

[0045] The second reaction monomer in step (2) is 1,4-butanediamine.

[0046] The sample obtained in step (4) is named: P1.

[0047] Figure 5 TEM images of a show that P1 exhibits a typical two-dimensional sheet-like morphology.

[0048] 2. Polymerization of isocyanate monomers and alcohol monomers - nucleophilic addition reaction The first reactant in step (1) is triphenylmethane triisocyanate; the solvent is toluene; the rotation speed is 300 rpm.

[0049] The second reactant in step (2) is ethylene glycol; the solvent is acetonitrile.

[0050] The rotation speed in step (3) is 400 rpm; the time is 60 minutes.

[0051] The pore size of the polytetrafluoroethylene filter membrane in step (4) is 0.1. m; Drying temperature: 70℃; Drying time: 12 hours; Name of the obtained sample: P2.

[0052] Figure 5 The TEM image of b shows that P2 exhibits a typical two-dimensional sheet-like morphology.

[0053] 3. Polymerization-curing reaction of epoxy resin monomers and amine monomers The first reactant in step (1) is glycerol epoxy resin; the solvent is dichloromethane.

[0054] The second reactant in step (2) is 1,2,3-propanetriamine; the solvent is water.

[0055] The rotation speed in step (3) is 400 rpm; the time is 80 minutes.

[0056] The drying temperature in step (4) was 40°C; the drying time was 6 hours; and the resulting sample was named P3.

[0057] Figure 5 The TEM image of c shows that P3 exhibits a typical two-dimensional sheet-like morphology.

[0058] 4. Polymerization of aldehyde and amine monomers - Schiff base reaction The first reactant in step (1) is pyromellitic aldehyde; solvent: toluene; concentration: 0.6 mol / L; volume: 5.0 mL.

[0059] The second monomer in step (2) is 1,4-butanediamine; the solvent is water; the concentration is 2.0 mol / L; and the volume is 2.3 mL.

[0060] The rotation speed in step (3) is 100 rpm; the time is 80 minutes.

[0061] The pore size of the polytetrafluoroethylene filter membrane in step (4) is 0.1. m; Drying temperature: 70℃; Drying time: 12 hours; The resulting sample is named: P4.

[0062] Figure 5 The TEM image of d shows that P4 exhibits a typical two-dimensional sheet-like morphology.

[0063] 5. Polymerization of vinyl aromatic monomers and thiol monomers - click chemi-addition reaction The first reactant monomer in step (1) is 1,3,5-trivinylbenzene; the solvent is o-xylene; and the temperature is 40°C.

[0064] The second reactant in step (2) is 1,3-propanedithiol; the solvent is an aqueous solution containing the photoinitiator.

[0065] The pore size of the polytetrafluoroethylene filter membrane in step (3) is 0.45. m; Drying temperature: 70℃; Drying time: 12 hours; Name of the obtained sample: P5.

[0066] Figure 5 The TEM image of e shows that P5 exhibits a typical two-dimensional sheet-like morphology.

[0067] 6. Polymerization-coordination reaction of imidazole monomers and metal salt monomers The first reactant in step (1) is 2-methylimidazole; the solvent is chloroform.

[0068] The second reactant in step (2) is zinc nitrate; the solvent is water.

[0069] The drying temperature in step (4) was 50°C; the drying time was 8 hours; and the resulting sample was named P6.

[0070] Figure 5 The TEM image of f shows that P6 exhibits a typical two-dimensional sheet-like morphology.

[0071] Example 2 Preparation of Quasi-Solid-State Electrolytes 1. Two-dimensional PEO-BTA nanosheets were prepared using dynamic micro-interface polymerization technology; 2. The above two-dimensional PEO-BTA nanosheets were added to anhydrous ethanol and ultrasonically dispersed to obtain a uniform dispersion with a mass concentration of 10 mg / mL. 3. Film formation using a blade coating process: The ethanol dispersion of the above-mentioned two-dimensional PEO-BTA nanosheets was used as the coating material. The blade coating speed was controlled at 80 mm / s, and the blade gap was set to 300 mm. m, after uniform coating to obtain a wet film, the wet film is then placed in a vacuum drying oven at 60℃ for 5 hours to obtain a large-area PEO-BTA dry film with excellent self-support and a smooth and defect-free film surface; 4. Cut the obtained dry membrane into circular sheets with a diameter of 16 mm, and immerse them in a 1.0 mol / L sodium hexafluorophosphate-1,2-dimethoxyethane electrolyte solution for 2 hours. After immersion, remove the membrane and gently wipe it with filter paper to remove excess droplets from the membrane surface, finally obtaining the gelled PEO-BTA quasi-solid electrolyte.

[0072] Figure 6 Image a shows a large-area PEO-BTA dry film prepared using a blade coating process. It can be clearly observed from the image that the PEO-BTA film exhibits high uniformity, with a smooth surface and no obvious defects.

[0073] Figure 6 b is a photograph of a 16 mm diameter circular sample cut from the aforementioned dry film. The image clearly shows that the cut film structure is intact and undamaged, with uniform thickness, fully demonstrating the excellent structural stability and machinability of the PEO-BTA dry film.

[0074] Figure 6 c represents the electrochemical impedance spectroscopy of the PEO-BTA quasi-solid-state electrolyte. Calculations show that this quasi-solid-state electrolyte exhibits a high room-temperature ionic conductivity of 1.05 mS / cm, demonstrating excellent ion transport performance and promising applications in energy storage fields such as sodium-ion batteries and lithium-ion batteries.

[0075] Compared to existing electrolyte membrane material preparation technologies such as in-situ polymerization and phase inversion, the two-dimensional polymer nanosheets prepared by this invention through dynamic micro-interface polymerization technology can be seamlessly integrated with film formation processes such as blade coating, vacuum filtration, roller coating, and spray coating. This combination of technologies allows for precise and flexible control of the thickness and size of the electrolyte membrane. Furthermore, the aforementioned film formation processes are highly compatible with existing lithium-ion and sodium-ion battery production lines, requiring no additional large-scale equipment modifications, demonstrating significant feasibility for mass production, and effectively reducing the overall cost during industrialization.

[0076] Furthermore, the quasi-solid electrolyte prepared based on this technical route has reached the international leading level in its core performance indicator, ionic conductivity, further highlighting the application advantages and industrialization value of this technology.

[0077] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A dynamic micro-interface polymerization method for two-dimensional polymer materials, characterized in that: Includes the following steps: (1) Add the first reactant monomer to the solvent and stir until the first reactant monomer is completely dissolved to obtain the first monomer solution; (2) Add the second reactant to the solvent and stir until the second reactant is completely dissolved to obtain a solution of the second reactant; (3) The second monomer solution is added to the reaction vessel, and the first monomer solution is injected into the second monomer solution under stirring. After the reaction is completed, a reaction mixture system is obtained. (4) After filtering, purifying and drying the reaction mixture, the two-dimensional polymer material is obtained.

2. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The first reactant in step (1) is at least one of the following: acyl chloride monomers, sulfonyl chloride monomers, isocyanate monomers, epoxy resin monomers, aldehyde monomers, vinyl aromatic monomers, or imidazole monomers; the acyl chloride monomer is trimesoyl chloride or cyclohexane-1,3,5-tricarboxyl chloride; the sulfonyl chloride monomer is 1,3,6-naphthalenetrisulfonyl chloride or 1,3,5-benzenetrisulfonyl chloride; the isocyanate monomer is triphenylmethane triisocyanate or toluene-2,6-diisocyanate; the epoxy resin monomer is epoxy silicone resin or glycerol epoxy resin; the aldehyde monomer is terephthalaldehyde or trimesoyl chloride; the vinyl aromatic monomer is 1,4-divinylbenzene or 1,3,5-trivinylbenzene; and the imidazole monomer is 2-methylimidazolium or benzimidazole. The solvent in step (1) is at least one of n-hexane, cyclohexane, n-heptane, isooctane, dichloromethane, chloroform, toluene, o-xylene, chlorobenzene or anisole; the concentration of the first monomer solution in step (1) is 0.10-3.00 mol / L.

3. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The stirring step in step (1) has a rotation speed of 100-900 rpm, a time of 10-90 minutes, and a temperature of 20-60℃.

4. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The second reactant in step (2) is at least one of an amine monomer, an alcohol monomer, a thiol monomer, a carboxylic acid monomer, or a metal salt monomer; the amine monomer is at least one of polyetheramine, 1,4-butanediamine, 1,2,3-propanetriamine, or ethylene glycol bis(3-aminopropyl) ether; the alcohol monomer is 1,3,5-pentanetriol or ethylene glycol; the thiol monomer is 1,3-propanedithiol or triazine trithiol; the carboxylic acid monomer is 1,3,5-pentanetricarboxylic acid or succinic acid; and the metal salt monomer is zinc nitrate or copper acetate. The solvent in step (2) is at least one of water, methanol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide or ionic liquid; the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-benzyl-3-methylimidazolium dicyandiamide; the concentration of the second monomer solution in step (2) is 0.10-5.00 mol / L.

5. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The stirring step in step (2) has a rotation speed of 100-900 rpm, a time of 10-90 minutes, and a temperature of 20-60℃.

6. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The stirring step in step (3) has a rotation speed of 100-400 rpm, a time of 20-80 minutes, and a temperature of 23-27℃.

7. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The volume ratio of the first monomer solution to the second monomer solution in step (3) is 1:5-5:

1.

8. The dynamic micro-interface polymerization method for two-dimensional polymer materials according to claim 1, characterized in that: The filter membrane used in step (4) of the above process has a pore size of 0.1-0.45 mm. The polytetrafluoroethylene filter membrane of m; the drying step in step (4) is at a temperature of 40-70℃ and a time of 6-12 hours; the purification step in step (4) is as follows: anhydrous ethanol is added to the crude product after vacuum filtration, and after magnetic stirring, vacuum filtration is performed, and the solid is collected and washed with ethanol.

9. A two-dimensional polymer material prepared using the preparation method according to any one of claims 1-8.

10. The application of the two-dimensional polymer material according to claim 9, characterized in that: The application of the two-dimensional polymer material in the preparation of quasi-solid electrolytes.

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